EP1541650B1 - Poudre à base de polyamide et son utilisation pour obtenir un revêtement antibactérien - Google Patents

Poudre à base de polyamide et son utilisation pour obtenir un revêtement antibactérien Download PDF

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Publication number
EP1541650B1
EP1541650B1 EP04292762A EP04292762A EP1541650B1 EP 1541650 B1 EP1541650 B1 EP 1541650B1 EP 04292762 A EP04292762 A EP 04292762A EP 04292762 A EP04292762 A EP 04292762A EP 1541650 B1 EP1541650 B1 EP 1541650B1
Authority
EP
European Patent Office
Prior art keywords
powder
article
polyamide
silver ions
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04292762A
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German (de)
English (en)
French (fr)
Other versions
EP1541650A1 (fr
Inventor
Adrien Lapeyre
Christian Gancet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema France SA
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Filing date
Publication date
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Priority to PL04292762T priority Critical patent/PL1541650T3/pl
Publication of EP1541650A1 publication Critical patent/EP1541650A1/fr
Application granted granted Critical
Publication of EP1541650B1 publication Critical patent/EP1541650B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • the present invention relates to a polyamide-based powder and its use for coating objects. It is useful in the processes of covering an object with a film resulting from the melting of a thin layer of powder previously deposited on the object. More specifically, the powder of the invention is a mixture of polyamide and silver ions encapsulated in a soluble ceramic.
  • the first method is electrostatic powdering, it consists in charging the static electricity powder and putting it in contact with the object to be covered connected to a zero potential.
  • the powder is injected into an electrostatic gun which will charge said powder by corona effect (also called crown effect), by triboelectrification or by a combination of the two.
  • the powder thus charged is projected onto the object to cover connected to a zero potential.
  • the object connected to a zero potential is quenched in a fluidized bed of charged powder. Inside the fluidized bed is powder that we want to cover the object.
  • This powder is in the form of small solid particles, for example between 0.01 and 1 mm, of any shape, which are in a fluidized state inside the bed in the presence of air or any other gas.
  • the powder may be charged by corona electrodes or by any device disposed inside and / or outside the fluidized bed for triboelectric charging.
  • the powder coated object is then placed in an oven at a temperature sufficient to melt coat the powder causing filming. For example for a polyamide 11 powder it is sufficient to heat to 220 ° C.
  • the second method consists in preheating the object to be coated at a temperature higher than the melting temperature of the powder. Once hot, the object is immediately immersed in a fluidized bed of the powder, the powder melts in contact with the hot object and films. A solid recovery is thus ensured. This process is also referred to as a "fluidized bed soaking method”. It is also possible alternatively of the latter method to project the powder on the hot object.
  • the powder paint of the present invention is useful in both processes.
  • the invention relates to the field of high performance coatings. These are generally intended to provide the surface protected many properties they are appearance or functional (resistance to corrosion, abrasion, chemical resistance, thermal and UV, low coefficient of friction .. .).
  • Bacteria are unicellular organisms that reproduce by division. Their size is a few microns. There are thousands of species of bacteria, of which about 200 are pathogenic for humans. Gram + bacteria, such as Staphylococcus aureus, and Gramous bacteria Escherichia coli, Pseudomonas aeruginosa and Legionella sp.
  • inorganic biocides have been introduced. These compounds are mainly zeolite type carriers, glass, ceramics or zirconium phosphate complexes exchanged with silver. In the presence of moisture, an ion exchange is created which allows the release of silver ions which are powerful biocides.
  • Their introduction into polymers in order to obtain powder coatings having antibacterial properties has been described in the prior art (patent US 6,432,416 and patent application JP 06025561 A ). This type of biocide does not migrate, which guarantees antibacterial properties on the surface throughout the lifetime of the polymer. It is known to be able to use these products in multiple applications such as for refrigerator grids (patent application WO 02-40180 ) or grids for cooking (patent application WO 00-51429 ).
  • the silver ions being very reactive, this type of biocide can easily interact with the polymers in which they are added as well as with the additives and fillers possibly contained in these polymers and cause color problems. It is therefore very important that they be perfectly stabilized. It is the nature of the inorganic support that plays this role. It is she who protects the silver species from the action of temperature or UV. It also controls the rate of release of silver ions. This rate must be sufficient to ensure effective but controlled antibacterial activity to avoid the release of silver into the polymer matrix and thus the resulting interactions. In the case of powder paints based on polyamides, the application temperatures, especially when they are applied by dipping, make the choice of the biocide very difficult.
  • the present invention relates to the use of a powder for coating objects, this powder comprising by weight 99.8 to 97% of at least one polyamide and 0.2 to 3% of a soluble ceramic in which are encapsulated silver ions.
  • This powder can be prepared by simply dry blending the constituents.
  • the invention also relates to this powder. That is, the invention relates to a powder comprising, by weight, 99.8 to 97% of at least one polyamide and 0.2 to 3% of a soluble ceramic in which silver ions are encapsulated.
  • Ceramic protects the silver ions from temperature during the application and use of the product, UV rays and other components present in the formulation. It is the presence of moisture on the surface of the coating, necessary for the development of bacteria, which causes the release of silver ions and thus the elimination of bacteria.
  • the invention also relates to objects having an antibacterial coating obtained by the use of the above powders.
  • the invention described above has many advantages.
  • the polyamide powder paint composition applied to a metal surface either by electrostatic powdering or by soaking in a fluidized bed or by hot spraying gives it durable antibacterial properties.
  • This composition contains an inorganic biocide using silver ions as the sole active metal species.
  • This powder paint has the advantage of being applied at temperatures above 300 ° C. without problems of undesirable coloring and without the intervention of zinc. The side reactions caused by the silver species are thus avoided by the choice of a encapsulation in a soluble ceramic that effectively protects the silver ions against the temperature, the UV but also the other compounds of the formulation.
  • This invention allows the use of an inorganic silver-based biocide alone in a polyamide powder coating that can be applied at temperatures above 300 ° C without problems of undesirable coloring of the surface.
  • the silver ions being the metal species which has the highest efficiency and thus the lowest MIC (minimum inhibition concentration), they guarantee the coating an optimal activity throughout the lifetime of the polymer.
  • this composition makes it possible to dispense with the interactions that may occur between the polymer chain and the zinc compounds when these are used in admixture with the polyamide.
  • oxide glasses As regards the soluble ceramic in which silver ions are encapsulated, by way of example, mention may be made of oxide glasses. This category includes the different chemical substances produced in the production of inorganic glasses.
  • glass here designates an amorphous, mineral, transparent, translucent or opaque substance, traditionally formed by melting the contributions of silica using a flux, such as a carbonate of an alkaline metal, of the boron oxide, etc., and with a stabilizer. The mass obtained is cooled to become rigid, without crystallization in the case of transparent glass or separated in the liquid phase, with controlled crystallization in the case of glass-ceramics.
  • This category includes the various chemical substances, other than the by-products or the impurities, which are formed during the production of the different glasses, and parallel incorporated in a vitreous composition. All glasses contain one or more of these substances, but few, if any, contain them all.
  • the constituents mentioned below are mainly present in the form of oxides, but some may also appear in the form of halides or chalcogenides, with multiple oxidation states or in more complex compounds. Other oxides or chemical compounds may also be present in traces.
  • the oxides of the first seven elements mentioned represent more than 95%, by weight, of the glass produced: Aluminum *; Boron*; Calcium*; Magnesium*; Potassium*; Silicon*; Sodium*; Antimony; Arsenic; Barium; Bismuth; Cadmium; Carbon; Cerium; cesium; Chromium; Cobalt; Copper; Germanium; Gold; holmium; Iron; Lanthanum; Lead; Lithium; Manganese; Molybdenum; neodymium; Nickel; Niobium; Nitrogen; Phosphorus; praseodymium; Rubidium; Selenium; Money; Strontium; Sulfur; Tellurium; Tin; Titanium; Tungsten; Uranium; Vanadium; Zinc; Zirconium.
  • the aliphatic polyamides can be chosen from PA 11, PA 12, aliphatic polyamides resulting from the condensation of an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having from 9 to 12 carbon atoms and the copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units 12.
  • the 11/12 copolyamides having more than 90% of units 11 or more than 90% of units 12 they result from the condensation of 1-undecanoic amino acid with lauryllactam (or the alpha omega amino acid in C 12 ).
  • PA 11 and PA 12 are advantageously used.
  • the polyamide powder has a particle size ranging from 10 to 1000 microns.
  • dry blend is used as opposed to a blend in which the thermoplastic polymer is in the molten state.
  • the usual mixers of the powdered products can be used, for example Henschel®. The mixing is done at normal temperature and pressure. The mixing time must be sufficient for the mixture to be homogeneous.
  • the proportion of silver ions in the soluble ceramic may be any as long as there are enough silver ions to achieve an antibacterial effect. It is advantageously between 1 and 10% by weight and preferably between 3 and 6%.
  • this powder comprises 99.5 to 99% by weight of at least one polyamide and 0.5 to 1% of a soluble ceramic in which silver ions are encapsulated.
  • the concentration is preferably of the order of 0.6%. It may be lower, but in this case we do not find the expected effectiveness on all the targeted bacteria.
  • the antimicrobial agent content is not necessarily 0.6%. It was chosen so as to obtain a compromise between the efficiency and the price of the product. It has also been determined in such a way as to minimize the risks that the release of the composition could have in an aquatic environment.
  • the powder of the invention may also include anti-UV additives, antioxidants, dyes, pigments, flame retardants, etc. These products are preferably incorporated in the polyamide before it is reduced to powder.
  • metal objects examples include aluminum, aluminum alloys, steel and its alloys. Possibly a surface pretreatment is performed on the object before coating it with powder. These are the classic pre-treatments used in the coating industry: phosphating, degreasing, shot blasting. One can also use a primary.
  • the invention also relates to this powder.
  • the composition of this powder, the nature and the proportions of its constituents are those described above for its use.
  • this composition is applied to previously defatted, blasted and coated steel plates with an adhesion primer.
  • the application can be done either by electrostatic spraying, or by hot spraying or by soaking in a fluidized bed.
  • the colorimetric coordinates of the coatings obtained are then measured by means of a spectrocolorimeter and compared with those of the corresponding commercial grade (that is to say the polyamide powder with its additives but not containing the antibacterial). or no change in color between the commercial grade and the additive grade, which can not be obtained (see example) when the support containing the silver is a zeolite or a zirconium phosphate.
  • the antibacterial properties are evaluated according to the JIS Z 2801-2000 standard, modified so as to make handling easier. The exact protocol is described below:
  • Glue the Gene Frame cells (polyethylene film whose edges are self-adhesive so as to adhere to the support) on the steel plates coated with the antibacterial polyamide to be tested at the rate of 2 cells per plate for a better reproducibility of the handling.
  • composition A 0.6% of sanitized BC A 21-41 is blended dry-blended into a commercial RILSAN® T gray 3362 (based on PA 11) using a Henshel rapid mixer to obtain a composition A.
  • the powder composition A obtained as well as the commercial grade T gray 3362 MAC are applied by dipping. This process consists in degreasing, blasting a steel plate and pneumatically spraying it with an epoxy adhesion primer, then preheating it at a temperature 300 ° C. The test piece thus prepared is immersed in a tank containing powder to be applied in fluidization.
  • the coating obtained from the patented composition has a good efficacy making it possible to reduce the bacterial population by more than 99.99% on the strains of E. coli, S. aureus and L. pneumophila.
  • compositions B, C, D are produced by incorporating into the dry blend respectively 0.6% of Sanitized BC A 21-41, 0.6% of Agion AK10D (zeolite exchanged with silver), and 0.6% of ALPHASAN RC5000 (silver-exchanged zirconium phosphate) in white ES grade 840 (PA 11 powder).
  • Compositions B, C and D and white commercial grade ES 840 are electrostatically applied. This process consists in degreasing, blasting and coating a steel plate with a pneumatic spraying epoxy adhesion primer. The powder to be applied is positively charged in a corona gun to be projected onto the specimen prepared as described above and connected to the ground.
  • the coating corresponding to the composition B obtained with the product of Sanitized AG (ceramic containing silver ions) has a very low colorimetric evolution compared to the products obtained from either the zeolite exchanged with silver or from the zirconium phosphate exchanged. to money.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP04292762A 2003-12-05 2004-11-24 Poudre à base de polyamide et son utilisation pour obtenir un revêtement antibactérien Expired - Lifetime EP1541650B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL04292762T PL1541650T3 (pl) 2003-12-05 2004-11-24 Proszek na bazie poliamidu i jego stosowanie w celu otrzymania powłoki przeciwbakteryjnej

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0314305A FR2863271B1 (fr) 2003-12-05 2003-12-05 Poudre a base de polyamide et son utilisation pour obtenir un revetement antibacterien
FR0314305 2003-12-05

Publications (2)

Publication Number Publication Date
EP1541650A1 EP1541650A1 (fr) 2005-06-15
EP1541650B1 true EP1541650B1 (fr) 2008-01-02

Family

ID=34508608

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Application Number Title Priority Date Filing Date
EP04292762A Expired - Lifetime EP1541650B1 (fr) 2003-12-05 2004-11-24 Poudre à base de polyamide et son utilisation pour obtenir un revêtement antibactérien

Country Status (11)

Country Link
EP (1) EP1541650B1 (da)
JP (1) JP4248484B2 (da)
KR (1) KR20050054850A (da)
CN (1) CN1282724C (da)
AT (1) ATE382669T1 (da)
CA (1) CA2487975C (da)
DE (1) DE602004011007T2 (da)
DK (1) DK1541650T3 (da)
ES (1) ES2298701T3 (da)
FR (1) FR2863271B1 (da)
PL (1) PL1541650T3 (da)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009016881A1 (de) * 2009-04-08 2010-10-14 Arkema France, S.A. Verfahren zum Herstellen eines dreidimensionalen Objekts unter Verwendung eines Kunststoffpulvers mit antimikrobiellen Eigenschaften und Kunststoffpulver mit antimikrobiellen Eigenschaften für ein derartiges Verfahren

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2877948B1 (fr) * 2004-11-12 2007-01-05 Arkema Sa Procede de synthese de poudres de polyamide
FR2946667B1 (fr) * 2009-06-16 2011-10-28 Arkema France Textile bacteriostatique a base de polyamide 11
FR2955864B1 (fr) 2010-02-01 2012-03-23 Arkema France Poudre a base de polyamide et procede de revetement d'objet par fusion de ladite poudre
FR3115042B1 (fr) * 2020-10-09 2023-01-06 Arkema France Procédé de préparation d’une composition de poudre de polyamides avec rendement optimisé

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4938958A (en) * 1986-12-05 1990-07-03 Shinagawa Fuel Co., Ltd. Antibiotic zeolite
US6432416B1 (en) * 1997-10-03 2002-08-13 Dupont Powder Coatings Usa, Inc. Anti-microbial power coating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009016881A1 (de) * 2009-04-08 2010-10-14 Arkema France, S.A. Verfahren zum Herstellen eines dreidimensionalen Objekts unter Verwendung eines Kunststoffpulvers mit antimikrobiellen Eigenschaften und Kunststoffpulver mit antimikrobiellen Eigenschaften für ein derartiges Verfahren

Also Published As

Publication number Publication date
JP4248484B2 (ja) 2009-04-02
FR2863271A1 (fr) 2005-06-10
JP2005171245A (ja) 2005-06-30
EP1541650A1 (fr) 2005-06-15
ES2298701T3 (es) 2008-05-16
CA2487975A1 (fr) 2005-06-05
DE602004011007T2 (de) 2008-12-24
DE602004011007D1 (de) 2008-02-14
ATE382669T1 (de) 2008-01-15
FR2863271B1 (fr) 2006-01-20
CA2487975C (fr) 2010-04-20
DK1541650T3 (da) 2008-05-13
KR20050054850A (ko) 2005-06-10
CN1282724C (zh) 2006-11-01
CN1637095A (zh) 2005-07-13
PL1541650T3 (pl) 2008-06-30

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